全文获取类型
收费全文 | 845篇 |
免费 | 50篇 |
国内免费 | 9篇 |
专业分类
化学 | 612篇 |
晶体学 | 5篇 |
力学 | 25篇 |
数学 | 138篇 |
物理学 | 124篇 |
出版年
2023年 | 9篇 |
2022年 | 8篇 |
2021年 | 19篇 |
2020年 | 13篇 |
2019年 | 35篇 |
2018年 | 14篇 |
2017年 | 7篇 |
2016年 | 27篇 |
2015年 | 35篇 |
2014年 | 37篇 |
2013年 | 60篇 |
2012年 | 71篇 |
2011年 | 59篇 |
2010年 | 34篇 |
2009年 | 38篇 |
2008年 | 60篇 |
2007年 | 54篇 |
2006年 | 45篇 |
2005年 | 36篇 |
2004年 | 39篇 |
2003年 | 38篇 |
2002年 | 29篇 |
2001年 | 9篇 |
2000年 | 3篇 |
1999年 | 13篇 |
1998年 | 7篇 |
1997年 | 10篇 |
1996年 | 10篇 |
1995年 | 6篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1991年 | 4篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1985年 | 2篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 5篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1976年 | 5篇 |
1973年 | 4篇 |
1971年 | 3篇 |
1970年 | 3篇 |
1968年 | 2篇 |
1966年 | 4篇 |
排序方式: 共有904条查询结果,搜索用时 15 毫秒
141.
Bagchi S Kim YS Charnley AK Smith AB Hochstrasser RM 《The journal of physical chemistry. B》2007,111(11):3010-3018
The linear infrared and two-dimensional infrared (2D IR) spectra in the amide-I region of N-acetyl tryptophan methyl amide (NATMA) in solvents of varying polarity are reported. The two amide-I transitions have been assigned unambiguously by using 13C isotopic substitution of the carbonyl group. The amide unit at the amino end shows a lower transition frequency in CH2Cl2 and methanol, while the acetyl end has a lower transition frequency in D2O. Multiple conformers exist in CH2Cl2 and methanol, but only one conformer is evident in D2O. The 2D IR cross peaks from the intermode coupling yield off-diagonal anharmonicities 2.5 +/- 0.5, 3.25 +/- 0.5, and 3.0 +/- 0.5 cm(-1) in CH2Cl2, methanol, and D2O, respectively, which by simple matrix diagonalization yield the coupling constants 8.0 +/- 0.5, 8.0 +/- 1.0, and 5.5 +/- 1.0 cm(-1). The major conformer in CH2Cl2 corresponds to a C7 structure, in agreement with that found in the gas phase [Dian, B. C.; Longarte, A.; Mercier, S.; Evans, D. A.; Wales, D. J.; Zwier, T. S. J. Chem. Phys. 2002, 117, 10688-10702] with intramolecular hydrogen bonding between the acetyl end C=O and the amino end N-H. The backbone dihedral angles (phi, psi) are determined to be in the ranges of (-55 +/- 5 degrees , 30 +/- 5 degrees ), (120 +/- 10 degrees , -20 +/- 10 degrees ), and (+/-160 +/- 10 degrees , +/-75 +/- 10 degrees ) in CH2Cl2, methanol, and D2O, respectively. 相似文献
142.
The electrochemistry of 2,6-dimethylbenzoquinone (DMBQ) has been characterized for three different systems: DMBQ freely solvated in aqueous buffer; DMBQ bound to a neutral, blocked cysteine (N-acetyl-L-cysteine methyl ester) and the resulting DMBQ-bCys compound solvated in aqueous buffer; and DMBQ bound to a small model protein denoted alpha(3)C. The goal of this study is to detect and characterize differences in the redox properties of the protein-ligated DMBQ relative to the solvated quinones. The alpha(3)C protein used here is a tryptophan-32 to cysteine-32 variant of the structurally defined alpha(3)W de novo protein (Dai et al. J. Am. Chem. Soc. 2002, 124, 10952-10953). The properties of alpha(3)C were recently described (Hay et al. Biochemistry 2005, 44, 11891-11902). DMBQ was covalently bound to bCys and alpha(3)C through a sulfur substitution reaction with the cysteine thiol. In contrast to the solvated DMBQ and DMBQ-bCys compounds, diffusion controlled electrochemistry of DMBQ-alpha(3)C showed well-behaved and fully reversible n = 2 oxidation/reduction with a peak separation of approximately 30 mV between pH 5 and 9. DMBQ-alpha(3)C could also be immobilized on a gold electrode modified with a self-assembled monolayer of 3-mercaptopropionoic acid, allowing the measurement, by cyclic voltammetry, of an apparent rate of electron transfer of 22 s(-1). The (cysteine) sulfur substitution significantly lowers one of the hydroquinone pKA's from 10.4 in DMBQ to 6.8 in DMBQ-bCys. This pKA is slightly elevated in DMBQ-alpha(3)C to 7.0 and the E1/2 at pH 7.0 is raised by 110 mV from +190 mV in DMBQ-bCys to +297 mV in DMBQ-alpha(3)C. 相似文献
143.
This report describes a method to simultaneously determine 11 low-molecular-weight (LMW) organic acids and 16 chlorinated acid herbicides within a single run by a portable CE system with contactless conductivity detection (CCD) in a poly(vinyl alcohol) (PVA)-coated capillary. Under the optimized condition, the LODs of CE-CCD ranged from 0.056 to 0.270 ppm, which were better than for indirect UV (IUV) detection of the 11 LMW organic acids or UV detection of the 16 chlorinated acid herbicides. Combined with an on-line field-amplified sample stacking (FASS) procedure, sensitivity enhancement of 632- to 1078-fold was achieved, with satisfactory reproducibility (RSDs of migration times less than 2.2%, and RSDs of peak areas less than 5.1%). The FASS-CE-CCD method was successfully applied to determine the two groups of acidic pollutants in two kinds of environmental water samples. The portable CE-CCD system shows advantages such as simplicity, cost effectiveness, and miniaturization. Therefore, the method presented in this report has great potential for onsite analysis of various pollutants at the trace level. 相似文献
144.
145.
Pudney CR Hay S Pang J Costello C Leys D Sutcliffe MJ Scrutton NS 《Journal of the American Chemical Society》2007,129(45):13949-13956
We have identified multiple reactive configurations (MRCs) of an enzyme-coenzyme complex that have measurably different kinetic properties. In the complex formed between morphinone reductase (MR) and the NADH analogue 1,4,5,6-tetrahydro-NADH (NADH4) the nicotinamide moiety is restrained close to the FMN isoalloxazine ring by hydrogen bonds from Asn-189 and His-186 as determined from the X-ray crystal structure. Molecular dynamic simulations indicate that removal of one of these hydrogen bonds in the N189A MR mutant allows the nicotinamide moiety to occupy a region of configurational space not accessible in wild-type enzyme. Using stopped-flow spectroscopy, we show that reduction of the FMN cofactor by NADH in N189A MR is multiphasic, identifying at least four different reactive configurations of the MR-NADH complex. This contrasts with wild-type MR in which hydride transfer occurs by environmentally coupled tunneling in a single kinetic phase [Pudney et al. J. Am. Chem. Soc. 2006, 128, 14053-14058]. Values for primary and alpha-secondary kinetic isotope effects, and their temperature dependence, for three of the kinetic phases in the N189A MR are consistent with hydride transfer by tunneling. Our analysis enables derivation of mechanistic information concerning different reactive configurations of the same enzyme-coenzyme complex using ensemble stopped-flow methods. Implications for the interpretation from kinetic data of tunneling mechanisms in enzymes are discussed. 相似文献
146.
Sample preparation techniques for the determination of trace residues and contaminants in foods 总被引:1,自引:0,他引:1
The determination of trace residues and contaminants in complex matrices, such as food, often requires extensive sample extraction and preparation prior to instrumental analysis. Sample preparation is often the bottleneck in analysis and there is a need to minimise the number of steps to reduce both time and sources of error. There is also a move towards more environmentally friendly techniques, which use less solvent and smaller sample sizes. Smaller sample size becomes important when dealing with real life problems, such as consumer complaints and alleged chemical contamination. Optimal sample preparation can reduce analysis time, sources of error, enhance sensitivity and enable unequivocal identification, confirmation and quantification. This review considers all aspects of sample preparation, covering general extraction techniques, such as Soxhlet and pressurised liquid extraction, microextraction techniques such as liquid phase microextraction (LPME) and more selective techniques, such as solid phase extraction (SPE), solid phase microextraction (SPME) and stir bar sorptive extraction (SBSE). The applicability of each technique in food analysis, particularly for the determination of trace organic contaminants in foods is discussed. 相似文献
147.
Senarath-Yapa MD Phimphivong S Coym JW Wirth MJ Aspinwall CA Saavedra SS 《Langmuir : the ACS journal of surfaces and colloids》2007,23(25):12624-12633
The fabrication, characterization, and implementation of poly(lipid)-coated, highly luminescent silica nanoparticles as fluorescent probes for labeling of cultured cells are described. The core of the probe is a sol-gel-derived silica nanoparticle, 65-100 nm in diameter, in which up to several thousand dye molecules are encapsulated (Lian, W.; et al. Anal. Biochem. 2004, 334, 135-144). The core is coated with a membrane composed of bis-sorbylphosphatidylcholine, a synthetic polymerizable lipid that is chemically cross-linked to enhance the environmental and chemical stability of the membrane relative to a fluid lipid membrane. The poly(lipid) coating has two major functions: (i) to reduce nonspecific interactions, based on the inherently biocompatible properties of the phosphorylcholine headgroup, and (ii) to permit functionalization of the particle, by doping the coating with lipids bearing chemically reactive or bioactive headgroups. Both functions are demonstrated: (i) Nonspecific adsorption of dissolved proteins to bare silica nanoparticles and of bare nanoparticles to cultured cells is significantly reduced by application of the poly(lipid) coating. (ii) Functionalization of poly(lipid)-coated nanoparticles with a biotin-conjugated lipid creates a probe that can be used to target both dissolved protein receptors as well as receptors on the membranes of cultured cells. Measurements performed on single nanoparticles bound to planar supported lipid bilayers verify that the emission intensity of these probes is significantly greater than that of single protein molecules labeled with several fluorophores. 相似文献
148.
The Finite Element Model Updating (FEMU) technique is an inverse method that enables to arrive at a complete solution to the problem of diffuse necking of a thick tensile specimen. Conventionally, FEMU relies on the identification of a phenomenological strain hardening law that inherently limits the accuracy of the method due to the predefined character of the adopted strain hardening law. A high-resolution multi-linear post-necking strain hardening model enables to describe more generically the actual strain hardening behaviour. A numerical concept study is used to scrutinise the identification of such a model using FEMU. It is shown that, unlike progressive identification strategies, a global identification strategy followed by a smoothing operation based on area conservation yields sufficiently accurate results. To study the experimental feasibility, the latter strategy is used to identify the post-necking strain hardening behaviour of a thick S690QL high-strength steel. To this purpose, a notched tensile specimen was loaded up to fracture, while the elongation was measured using Digital Image Correlation (DIC). It is shown that the global identification strategy suffers from experimental noise associated with DIC and the load signal. 相似文献
149.
Jun Cheng P. Hu Peter Ellis Sam French Gordon Kelly C. Martin Lok 《Surface science》2009,603(17):2752-2758
Transition metals are often introduced to a catalyst as promoters to improve catalytic performance. In this work, we study the promotion effect of transition metals on Co, the preferred catalytic metal for Fischer–Tropsch synthesis because of its good compromise of activity, selectivity and stability, for ethylene chemisorption using density functional theory (DFT) calculations, aiming to provide some insight into improving the α-olefin selectivity. In order to obtain the general trend of influence on ethylene chemisorption, twelve transition metals (Zr, Mn, Re, Ru, Rh, Ir, Ni, Pd, Pt, Cu, Ag and Au) are calculated. We find that the late transition metals (e.g. Pd and Cu) can decrease ethylene chemisorption energy. These results suggest that the addition of the late transition metals may improve α-olefin selectivity. Electronic structure analyses (both charge density distributions and density of states) are also performed and the understanding of calculated results is presented. 相似文献
150.
Reza Latifi Mojtaba Bagherzadeh Prof. Dr. Sam P. de Visser Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(27):6651-6662
A series of hydrogen‐abstraction barriers of a nonheme iron(IV)–oxo oxidant mimicking the active species of taurine/α‐ketoglutarate dioxygenase (TauD) are rationalized by using a valence‐bond curve‐crossing diagram (see figure). It is shown that the barriers correlate with the strength of the C? H bond. Furthermore, electronic differences explain the differences between nonheme and heme iron(IV)–oxo hydrogen‐abstraction barriers.